Catalyst coatings having metal oxide crystallites

ABSTRACT

Disclosed in certain implementations is a catalysis composition that includes a metal catalyst and a support material impregnated with the metal catalyst.

CROSS REFERENCE TO RELATED APPLICATION

This application claims the benefit of priority of U.S. ProvisionalPatent Application No. 61/897,557, filed Oct. 30, 2013, which is herebyincorporated by reference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates to a method and apparatus for cleaning theatmosphere. More particularly, the invention relates to a substrate suchas a motor vehicle radiator including pollution treating compositionlayered thereon.

BACKGROUND OF THE INVENTION

Atmospheric pollution is a concern of increasing importance as thelevels of various atmospheric pollutants continue to increase. Oneprimary pollutant of concern is ozone.

Ozone is a molecule that consists of three oxygen atoms.Naturally-occurring ozone is formed miles above the earth in thestratosphere. This ozone layer is responsible for absorbing the majorityof the sun's harmful ultraviolet radiation. Unfortunately, the ozone atground level is a health risk and the major component of smog. Thisground level ozone is the cause of many adverse effects, such asirritation of and damage to a subject's lungs, eyes, nose and throat.Ground level ozone is produced by the reactions of nitrogen oxides andvolatile organic compounds in the presence of direct sunlight. The mainsources of nitrogen oxide and volatile organic compound gases are mobileemissions, industrial factories, electrical plants, chemical solvents,and gasoline vapors.

Typical pollution control measures are directed toward removing nitrogenoxides and volatile organic compounds at emission sources. Pollutioncontrol is also performed by direct treatment of ozone at ground levelutilizing vehicle heat exchangers. In these processes, ozone in the airthat passes over catalyst coated surfaces, such as radiators, convertozone molecules into oxygen molecules. These processes capitalize on thelarge volume of air that passes through a vehicle's radiator.

There continues to be a need in the art for methods and compositions foreffectively treating ground level pollution. These methods andcompositions should exhibit long term performance and efficientmanufacturing operations.

SUMMARY

It is an object of certain implementations of the disclosure to providea catalyst composition to treat pollutants in the atmosphere.

It is an object of certain implementations of the disclosure to providea substrate including a catalyst composition to treat pollutants in theatmosphere.

It is an object of certain implementations of the disclosure to providea heat exchanger including a catalyst composition to treat pollutants inthe atmosphere.

It is an object of certain implementations of the disclosure to providean automobile radiator including a catalyst composition to treatpollutants in the atmosphere.

It is an object of certain implementations of the disclosure to providea method of preparing a catalyst composition to treat pollutants in theatmosphere.

It is an object of certain implementations of the disclosure to providea method of preparing a substrate including a catalyst composition totreat pollutants in the atmosphere.

It is an object of certain implementations of the disclosure to providea method of preparing a heat exchanger including a catalyst compositionto treat pollutants in the atmosphere.

It is an object of certain implementations of the disclosure to providea method of preparing an automobile radiator including a catalystcomposition to treat pollutants in the atmosphere.

The above objects and others are met by the present disclosure, which incertain implementations is directed to a catalysis composition includinga metal catalyst and a support material impregnated with the metalcatalyst. In certain implementations, the catalyst composition has adeactivation factor of at least 0.5.

In certain implementations, the disclosure is directed to a catalysiscomposition including a metal catalyst and a support material includingsurface hydroxyl groups, wherein the metal catalyst is impregnated inthe support material in an amount of about 0.5 atoms to about 2.5 atomsper surface hydroxyl group.

In certain implementations, the disclosure is directed to a catalysiscomposition including a metal catalyst and a support material, whereinthe metal catalyst is impregnated in the support material in an amountranging from about 10% to about 20% metal atoms by mass (e.g., masspercent of overall catalysis composition).

In certain implementations, the disclosure is directed to a catalysiscomposition including a metal catalyst and a support material, whereinthe metal catalyst is impregnated in the support material in an amountranging from about 10% to about 25% metal atoms by mass.

In certain implementations, the disclosure is directed to a catalysiscomposition including a metal catalyst and a support material, whereinthe metal catalyst is impregnated in the support material in an amountranging from about 5% to about 30% metal atoms by mass.

In certain implementations, the disclosure is directed to a catalysiscomposition including a metal catalyst and a support material, whereinthe metal catalyst is impregnated in the support material in an amountranging from about 12% to about 18% metal atoms by mass.

In certain implementations, the disclosure is directed to a catalysisdevice including an automobile radiator and an ozone catalyst coating atleast partially layered on the radiator, the catalyst coating includinga metal catalyst and a support material impregnated with the ozonecatalyst. In certain implementations, the coating has a deactivationfactor of at least 0.5.

In certain implementations, the disclosure is directed to a catalysisdevice consisting essentially of an automobile radiator and an ozonecatalyst coating at least partially layered on the radiator, wherein thecatalyst coating including a metal catalyst and a support materialimpregnated with the ozone catalyst. In certain implementations, thecatalyst coating has a deactivation factor of at least 0.5.

In certain implementations, the disclosure is directed to a catalysisdevice including an automobile radiator and a manganese oxide catalystcoating (e.g., derived from manganese acetate) at least partiallylayered on the radiator, wherein the catalyst coating including themanganese oxide catalyst (e.g., derived from manganese acetate), asupport material impregnated with the metal catalyst, wherein the metalcatalyst is impregnated in the support material in an amount rangingfrom about 12% to about 18% metal atoms by mass.

In certain implementations, the disclosure is directed to a catalysisdevice consisting essentially of an automobile radiator and a manganeseoxide catalyst coating (e.g., derived from manganese acetate) at leastpartially layered on the radiator, wherein the catalyst coatingincluding the manganese oxide catalyst (e.g., derived from manganeseacetate), a support material impregnated with the metal catalyst,wherein the metal catalyst is impregnated in the support material in anamount ranging from about 12% to about 18% metal atoms by mass.

In certain implementations, the disclosure is directed to a method ofpreparing a catalyst composition including mixing particulate supportmaterial in a solution of a metal catalyst to obtain a deactivationfactor of the composition of at least 0.5.

In certain implementations, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering anozone catalyst coating on an automobile radiator, wherein the catalystcoating including an ozone catalyst and a support material impregnatedwith the catalyst and the catalyst has a deactivation factor of at least0.5.

In certain implementations, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering anozone catalyst coating on an automobile radiator, wherein the catalystcoating including an ozone catalyst, a support material impregnated withthe catalyst, the catalyst has a deactivation factor of at least 0.5 andthe radiator does not include an additional catalyst layer or supportlayer.

In certain implementations, the disclosure is directed to a method ofpreparing a catalyst composition including mixing particulate supportmaterial in a solution of a metal catalyst wherein the catalyst isimpregnated in the support material in an amount ranging from about 10%to about 20% metal atoms by mass.

In certain implementations, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering amanganese oxide catalyst coating (e.g., derived from manganese acetate)on an automobile radiator, wherein the catalyst coating including ametal catalyst and a support material impregnated with the catalyst andthe catalyst has a deactivation factor of at least 0.5.

In certain implementations, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering amanganese oxide catalyst coating (e.g., derived from manganese acetate)on an automobile radiator, wherein the catalyst coating including ametal catalyst, a support material impregnated with the catalyst, theradiator does not include an additional catalyst layer or support layerand the catalyst has a deactivation factor of at least 0.5.

In certain implementations, the disclosure is directed to a method ofcleaning the atmosphere including contacting a composition as disclosedherein with an airstream including a pollutant and catalyzing thepollutant to a less toxic compound.

In certain implementations, the disclosure is directed to a method ofcleaning the atmosphere including contacting a device as disclosedherein with an airstream including a pollutant and catalyzing thepollutant to a less toxic compound.

In certain implementations, the disclosure is directed to a method ofcleaning the atmosphere including operating an automobile including adevice as disclosed herein.

In certain implementations, the disclosure is directed to an automobileincluding a device as disclosed herein.

In certain implementations, the disclosure is directed to an automobilepart including a composition as disclosed herein.

In certain implementations, a catalysis composition includes a metaloxide catalyst and a support material impregnated with the metal oxidecatalyst. The metal oxide catalyst is impregnated in the supportmaterial such that at least about 15% of a total number of metal atomsin the metal oxide catalyst are detectable by surface x-rayphotoelectron spectroscopy.

In certain implementations, a method includes providing a slurry of acatalysis composition, the catalyst composition including a metal oxidecatalyst and a support material impregnated with the metal oxidecatalyst. The metal oxide catalyst is impregnated in the supportmaterial such that at least about 15% of a total number of metal atomsin the metal oxide catalyst are detectable by surface x-rayphotoelectron spectroscopy. The method further includes coating theslurry onto a substrate to produce a catalyst layer.

In certain implementations, a catalysis composition includes a metaloxide catalyst and a support material impregnated with the metal oxidecatalyst such that a cumulative pore volume of the catalysis compositionis at least about 0.70 mL/g.

In certain implementations, a method includes providing a slurry of acatalysis composition, the catalysis composition including a metal oxidecatalyst a support material impregnated with the metal oxide catalystsuch that a cumulative pore volume of the catalysis composition is atleast about 0.70 mL/g. The method further includes coating the slurryonto a substrate to produce a catalyst layer.

In certain implementations, a catalysis composition includes a metaloxide catalyst and a support material impregnated with the metal oxidecatalyst such that an x-ray diffraction spectrum of the catalysiscomposition includes at least one characteristic peak including at leastone of a manganosite peak, pyrolusite peak, a bixbyite peak, or ahausmannite peak.

In certain implementations, a method includes providing a slurry of acatalysis composition, the catalysis composition including a metal oxidecatalyst and a support material impregnated with the metal oxidecatalyst such that an x-ray diffraction spectrum of the catalysiscomposition includes at least one characteristic peak including at leastone of a manganosite peak, pyrolusite peak, a bixbyite peak, or ahausmannite peak. The method further includes coating the slurry onto asubstrate to produce a catalyst layer.

In certain implementations, a catalysis composition includes a metaloxide catalyst and a support material impregnated with the metal oxidecatalyst such that the catalysis composition, when coated onto asubstrate and contacted with an airstream having an initial ozoneconcentration, is adapted to convert ozone within the airstream suchthat a final ozone concentration of the airstream is reduced by greaterthan 30% of the initial ozone concentration after the catalysiscomposition is contacted with the airstream.

In certain implementations, a method includes contacting a catalystlayer with an airstream. The catalyst layer includes a support materialimpregnated with a manganese oxide catalyst. The airstream has aninitial ozone concentration prior to contacting the catalyst layer, andthe airstream has a final ozone concentration after contact the catalystlayer, the final ozone concentration being reduced by greater than 30%of the initial ozone concentration.

In certain implementations, a catalysis composition includes a metaloxide catalyst and a support material impregnated with the metal oxidecatalyst. The catalyst composition further includes a first binder and asecond binder such that, after coating the catalysis composition onto asubstrate, an ultrasonic washcoat adhesion weight loss of the substrateis less than 1.60%.

In certain implementations, a method includes providing a slurry of acatalysis composition, the catalysis composition including a metal oxidecatalyst, a support material impregnated with the metal oxide catalyst,a first binder, and a second binder. The method further includes coatingthe slurry onto a substrate to produce a catalyst layer. After coatingthe catalysis composition onto the substrate, an ultrasonic washcoatadhesion weight loss of the substrate is less than 1.60%.

In certain implementations, the catalysis composition further includesparticles, wherein the particles include one or more of aluminumparticles, graphite particles, silicon carbide particles, or sapphireparticles. In certain implementations, the particles are in a form offlakes. In certain implementations, an average size of the particlesranges from about 1 micrometer to about 30 micrometers. In certainimplementations, an average size of the particles ranges from about 1micrometer to about 10 micrometers.

In certain implementations, a catalysis device includes an automobilecomponent and any of the aforementioned catalysis compositions (orimplementations thereof described herein) coated onto the automobilecomponent.

The term “atmosphere” is defined herein as the mass of air surroundingthe earth. The term “ambient air” shall mean the atmosphere which isdrawn or forced towards the outer surface of a composition or device asdisclosed herein.

The term “automobile” means any wheeled or unwheeled motorized machineor vehicle for (i) transporting of passengers or cargo or (ii)performing tasks such as construction or excavation moving. Vehicles canhave, e.g., at least 2 wheels (e.g., a motorcycle or motorized scooter),at least 3 wheels (e.g., an all-terrain vehicle), at least 4 wheels(e.g., a passenger automobile), at least 6 wheels, at least 8 wheels, atleast 10 wheels, at least 12 wheels, at least 14 wheels, at least 16wheels or at least 18 wheels. The vehicle can be, e.g., a bus, refusevehicle, freight truck, construction vehicle, heavy equipment, militaryvehicle or tractor. The vehicle can also be a train, aircraft,watercraft, submarine or spacecraft.

The term “radiator” means an apparatus to effect cooling to anassociated device through heat exchange.

The term “aged % conversion” means the percent conversion after a timerelative to the useful life of the device (e.g., exposure to theequivalent of 150,000 miles of on-road driving for an automobilecomponent).

The term “deactivation factor” means the ratio of the aged % conversionof a pollutant (e.g., ozone to oxygen) by a composition or device of thepresent invention to the fresh % conversion measured at conditions of800,000 hr⁻¹ space velocity and 75° C. In certain implementations, thedeactivation factor is calculated based on an ozone catalysiscomposition as disclosed herein coated on an automobile radiator. Theradiator may have, e.g., a 26 mm depth and 49 cells per square-inch(cpsi) or may have a 16 mm depth and 63 cpsi. In other implementations,the radiator may include a frame forming a window, a plurality oftubular conduits within the window for carrying a coolant and finsbetween the conduits having louvers formed therein.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features of the present disclosure, their nature,and various advantages will become more apparent upon consideration ofthe following detailed description, taken in conjunction with theaccompanying drawings, in which:

FIG. 1 is a side schematic view of a truck including components that maybe coated with a catalyst layer in accordance with an implementation;

FIG. 2 depicts a side cross-sectional view of an automobile radiator-airconditioning condenser assembly in accordance with an implementation;

FIG. 3 depicts a partial perspective view of a radiator with fins coatedwith a catalyst layer in accordance with an implementation;

FIG. 4 depicts a cross sectional view of a catalyst layer deposited on asolid substrate in accordance with an implementation;

FIG. 5 is a micrograph of a catalyst layer coating on an aluminumradiator surface in accordance with an implementation;

FIG. 6A is a plot showing deactivation factors for catalysts prepared inaccordance various example implementations;

FIG. 6B is another plot showing deactivation factors for catalystsprepared in accordance various example implementations;

FIG. 7A is an x-ray diffraction spectrum of an alumina support;

FIG. 7B is an x-ray diffraction spectrum of a catalyst preparedaccording to an implementation;

FIG. 7C is an x-ray diffraction spectrum of a catalyst preparedaccording to another implementation; and

FIG. 8 is a flow diagram illustrating a method for producing a catalystdevice in accordance with an implementation.

DETAILED DESCRIPTION

The present disclosure is directed to a compositions and methods oftreating pollutants. In one implementation, the disclosure is directedto a surface treatment of a heat exchange device (e.g., an automobileradiator) so that pollutants contained in ambient air may be readilyconverted to less harmful compounds. The present disclosure can beadapted for the conversion of hydrocarbons, volatile organic compounds(e.g., aromatics, aldehydes, carboxylic acids, etc.), ozone and carbonmonoxide into less harmful compounds such as oxygen, carbon dioxide andwater vapor.

In heat exchanger implementations, the flow of ambient air there throughmay be treated in accordance with the present invention. In certainaspects of the disclosure, the outer surface of the heat exchange deviceis capable of catalytically converting pollutants to less harmfulcompounds without adversely affecting the heat exchange activity of thedevice.

In other aspects of the disclosure, the heat exchanger provides anacceptable catalytic activity that is maintained over the useful life ofthe device. In other aspects of the disclosure, the intended activitymay be obtained with a single coat of catalytic material onto thesubstrate (e.g., the heat exchanger).

In certain implementations, the present disclosure is directed to acatalysis composition including a metal catalyst and a support materialimpregnated with the metal catalyst. In certain implementations, thedeactivation factor is least 0.5.

The catalysis compositions disclosed herein may treat a pollutant, e.g.,selected from the group consisting of ozone, hydrocarbons, volatileorganic compounds (e.g., aromatics, aldehydes, carboxylic acids, etc.),carbon dioxide, carbon monoxide and nitrous oxides (e.g., nitric oxideand nitrogen dioxide). For example, the catalysis composition mayconvert ozone to oxygen; carbon dioxide to water; carbon monoxide tocarbon dioxide; or nitrous oxides to nitrogen or nitrate.

The metal of the catalysis composition disclosed herein may be a basemetal. The base metal may be, e.g., selected from the group consistingof iron, copper, chromium, zinc, manganese, cobalt, nickel, compoundscontaining the same and combinations thereof.

In other implementations, the metal of the catalysis composition asdisclosed herein is a precious metal. The precious metal may be, e.g.,selected from the group consisting of platinum, palladium, rhodium,ruthenium, gold, silver, compounds containing the same and combinationsthereof.

In one implementation, the metal is manganese which may be derived froma manganese acetate precursor.

The support material can be a high surface area support material. Incertain implementations, the surface area of the support material has asurface area of at least about 50 m²/g; at least about 100 m²/g; fromabout 50 m²/g to about 5000 m²/g or from about 100 m²/g to about 300m²/g.

The surface area of the material may be determined by the BET(Brunauer-Emmett-Teller) method according to DIN ISO 9277:2003-05. Thespecific surface area is determined by a multipoint BET measurement inthe relative pressure range from 0.05-0.3 p/p₀.

In other implementations, the support material has a large pore volume.In certain implementations, the support material has an average porevolume ranging from about 0.5 mL/g to about 3 mL/g, about 0.7 mL/g toabout 1.2 mL/g, about 0.8 mL/g to about 1.5 mL/g, about 0.8 mL/g toabout 2 mL/g, about 0.8 mL/g to about 2 mL/g, about 1.2 mL/g to about 2mL/g, or about 1.5 mL/g to about 2 mL/g.

The material utilized as the support material can be a refractory oxideor any other suitable material. In certain implementations, the materialis metal organic framework.

For example, the support material may include, e.g., a material selectedfrom the group consisting of ceria, lanthana, alumina, titania, silica,zirconia, carbons, metal organic framework, clay, zeolites andcombinations thereof.

In one implementation, the support material is selected from the groupconsisting of alumina, silica and combinations thereof. The alumina andsilica may be in a ratio (w/w) of about 1:99 to 99:1; about 1:50 to50:1; about 10:1 to about 30:1 or about 19:1.

In one implementation, the support material may have surface hydroxylgroups. In such an implementation, the catalyst may be impregnated inthe support material, e.g., in an amount of at least 0.5 atom persurface hydroxyl group; in an amount of at least 1.0 atom per surfacehydroxyl group; in an amount of about 0.5 atom to about 2.5 atoms persurface hydroxyl group or in an amount of about 1 atom to about 1.5atoms per surface hydroxyl group.

In another implementation, the metal component of the catalysiscomposition may be in an amount, e.g., ranging from about 5% to about30% by mass, about 10% to about 25% by mass, or about 12% to about 18%by mass.

In certain implementations of the disclosure, a portion of the catalystis in amorphous form. In certain aspects, at least 50%, at least 60%, atleast 75% or at least 85% of the catalyst is in amorphous form.

The catalyst composition of the present invention may be usedindependent of other materials to treat the atmosphere or can becombined with other materials. In one implementation, the composition iscoated onto a substrate. The substrate can be, e.g., a heat exchangersuch as an automobile radiator or a battery cooling device.

In certain implementations, the catalysis composition of the presentdisclosure may include an acid additive. The acid additive may be anorganic acid or any other suitable acid. For example, the acid may beselected from the group consisting of tartaric acid, malic acid, fumaricacid, acetic acid, citric acid and a combination thereof.

The compositions and devices of the present invention may have adeactivation factor of at least 0.5; at least 0.55, at least 0.6 atleast 0.65, at least 0.7 or at least 0.8. In one implementation, thedeactivation factor is measured with the catalysis composition coatedonto a radiator.

In certain implementations, the deactivation factor of the device is atleast 0.55, at least 0.60 or at least 0.65 based on a radiator (e.g., anautomobile radiator) with 26 mm depth and 49 cpsi. In otherimplementations, these parameters are obtained on a radiator is fittedwith louvers and fins, e.g., in the form including a frame forming awindow, a plurality of tubular conduits within the window for carrying acoolant and fins between the conduits having louvers formed therein.

In certain implementations, the deactivation factor of the device is atleast 0.50 at least 0.55 or at least 0.60 based on a radiator (e.g., anautomobile radiator) with 16 mm depth and 63 cpsi. In otherimplementations, these parameters are obtained on a radiator is fittedwith louvers and fins, e.g., in the form including a frame forming awindow, a plurality of tubular conduits within the window for carrying acoolant and fins between the conduits having louvers formed therein.

The catalysis composition (e.g., ozone catalyst) of the presentinvention may be layered on from about 10% to about 100% of thesubstrate (e.g. radiator) surface or from about 60% to about 100% of theradiator surface.

The coating may be any suitable thickness, e.g., from about 1 to about100 micrometers, from about 10 to about 50 micrometers or from about 15to about 35 micrometers.

In certain aspects of the disclosure, the catalysis composition is theonly material layered onto the substrate. In other implementations, thecatalysis composition is the only catalysis material layered onto thesubstrate.

In certain aspects, there may be an overlayer on the catalyst coating oran underlayer between the substrate (e.g., radiator) and the catalystcoating. The underlayer or over layer may be a protective coat, anadhesion coat or an additional catalysis coat. The adhesion coat may bea latex material or an acrylic material. The protective coat may containa protective substance which is stable at elevated temperatures (e.g.,up to 120° C.) and may be resistant to chemicals, salts, dirt and othercontaminants which may adversely affect the catalyst composition. Theprotective material may be, e.g., a plastic material such aspolyethylene, polypropylene, polytetrafluoroethylene or a combinationthereof.

When the catalysis composition is coated onto an automobile radiator,the device may have, e.g., less than about 6% impact on coolingefficiency as compared to an uncoated radiator, less than about 5%impact on cooling efficiency as compared to an uncoated radiator or lessthan about 3% impact on cooling efficiency as compared to an uncoatedradiator.

In other implementations when the catalysis composition is coated ontoan automobile radiator, the device may have, e.g., a washcoat weightloss of less than about 6%, or less than about 3% based on an ultrasonicadhesion test.

In further implementations when the catalysis composition is coated ontoan automobile radiator, the device may have, e.g., less than about a 20%increase in pressure drop in a coated device as compared to a non-coateddevice, less than about a 15% increase in pressure drop in a coateddevice as compared to a non-coated device or less than about a 10%increase in pressure drop in a coated device as compared to a non-coateddevice.

The catalysis composition of the present invention may have a dispersionof catalyst, e.g., of from about 50% to about 95% or from about 60% toabout 80% of manganese oxide crystallite domains measured less than 30nanometers using the primary crystallite dimension of the domains withinthe high surface area support structure based on transmission electronmicroscopy.

In other implementations, the catalysis composition of the presentinvention may have a dispersion of catalyst, e.g., of from about 50% toabout 95% or from about 60% to about 80% of manganese oxide crystallitedomains measured less than 15 nanometers using the primary crystallitedimension of the domains within the high surface area support structurebased on transmission electron microscopy.

In certain implementations, the disclosure is directed to a physicalmixture of metal oxide catalysts particles and high surface area supportparticles such that separate domains of metal oxide and support canfunction independently as catalyst and aging protection respectively.

In other implementations, the disclosure is directed to an alloy ofmetal oxide catalysts and high surface area support such that thefunction of each material is inseparable from the other.

In other implementations, the disclosure is directed to a high surfacearea support particle which is in surface contact either within the porestructure and/or externally with small (<100 nm) domains of metal oxidecatalysts such that separate domains of metal oxide can functionindependently as catalyst and are provided protection from agingmechanisms within the support material.

In other implementations, the disclosure is directed to a high surfacearea support particle which is externally coated with a porous shellstructure of metal oxide catalyst material such that the metal oxidecatalyst function is external to the support providing a high surfacearea interior to the composite particle.

In other implementations, the disclosure is directed to a high surfacearea support which is encompassing a metal oxide particle in a coatinglayer such that the metal oxide catalyst is entirely surrounded by aprotective high surface area support material.

The present disclosure is also directed to methods of preparing acatalysis device including at least partially layering an ozone catalystcoating on an automobile radiator, wherein the catalyst coatingincluding an ozone catalyst, a support material impregnated with thecatalyst and the catalyst has a deactivation factor of at least 0.5.

In other implementations, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering anozone catalyst coating on an automobile radiator, wherein the catalystcoating including an ozone catalyst, a support material impregnated withthe catalyst, the catalyst has a deactivation factor of at least 0.5 isin amorphous form and the radiator does not include an additionalcatalyst layer or support layer.

The certain aspects, the coating step may include, e.g., spraying,powder coating, dip coating, electroplating, or electrostaticing aparticulate support material in a solution of the catalyst onto theradiator. The solution may also include other agents such as asurfactant.

In a further implementation, the disclosure is directed to a method ofpreparing a catalyst composition including mixing particulate supportmaterial in a solution of a metal catalyst wherein the catalyst isimpregnated in the support material in an amount of about 0.5 atoms toabout 2.5 atoms per surface hydroxyl group of the support material.

In another implementation, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering amanganese acetate catalyst coating on an automobile radiator, whereinthe catalyst coating including a metal catalyst and a support materialimpregnated with the catalyst and the catalyst has a deactivation factorof at least 0.5.

In another implementation, the disclosure is directed to a method ofpreparing a catalysis device including at least partially layering amanganese acetate catalyst coating on an automobile radiator, whereinthe catalyst coating including a metal catalyst, a support materialimpregnated with the catalyst, the radiator does not include anadditional catalyst layer or support layer and the catalyst has adeactivation factor of at least 0.5.

In another aspect, a catalysis composition includes a catalyst and asupport material impregnated with the catalyst, such that the catalysiscomposition, when coated onto a substrate and contacted with anairstream having an initial ozone concentration, is adapted to convertozone within the airstream such that a final ozone concentration of theairstream is reduced by greater than 30% of the initial ozoneconcentration after the catalysis composition is contacted with theairstream, and the catalysis composition has a deactivation factor of atleast about 0.5.

In another aspect, a catalysis composition includes a catalyst and asupport material impregnated with the catalyst, such that the catalysiscomposition, when coated onto a substrate and contacted with anairstream having an initial ozone concentration, is adapted to convertozone within the airstream such that a final ozone concentration of theairstream is reduced by greater than 30% of the initial ozoneconcentration after the catalysis composition is contacted with theairstream. The initial ozone concentration ranges from about 0.1 ppm toabout 1.2 ppm, a space velocity of the airstream ranges from about200,000 hr⁻¹ to about 800,000 hr⁻¹, and a temperature of the airstreamis maintained within a range of about 70° C. to about 80° C.

One aspect of the present disclosure is directed to a method of cleaningthe atmosphere including contacting a composition or device as disclosedherein with an airstream including a pollutant and catalyzing thepollutant to a less toxic compound.

The device may be part of an automobile and the contacting withairstream is performed by operating the automobile.

The present disclosure is also directed to automobiles or automobileparts incorporating a composition or device as disclosed herein. Theautomobile part may be, e.g., selected from the group consisting ofvehicle paint, wheel wells, bumpers, air conditioning components,grilles, fans, blades, shrouds, shutters, turbo intercoolers, gear boxcoolers, battery coolers, front end components, and a hood liner.

FIG. 1 illustrates a truck 100 schematically containing a variety ofatmosphere contacting surfaces. The vehicle includes a grille 102, anair conditioner condenser 104, a radiator 106, and a radiator fan 108.These components are examples of automobile components that can becoated with the catalysis compositions disclosed herein. The airconditioning condenser 104 includes a front surface 104A and a side 105Bsurface, and the radiator 106 includes a front surface 106A and a sidesurface 106B. Each of these surfaces are located within a housing 110 ofthe truck. They are typically under the hood of the truck between thefront 112 of the truck and an engine 114. The air conditioner condenser104 and the radiator 106 can be directly or indirectly supported by thehousing 110 or a frame (not shown) within the housing 110. One or moreof these components may be coated with the catalysis compositionsdisclosed herein.

FIG. 2 depicts a side cross-sectional view of an automobile radiator-airconditioning condenser assembly in accordance with an implementation.The automobile includes a frame 200, which may be the same as the frame110 described with respect to FIG. 1. A front end of the automobileincludes a grille 202, which may be the same as the grille 102 describedwith respect to FIG. 1, and which is supported on the front of the frame200. An air conditioner condenser 204, a radiator 206, and a radiatorfan 208 may be located within the frame 200, and may be the same astheir identically named counterparts of FIG. 1. One or more of thesecomponents may be coated with the base metal catalyst layers disclosedherein.

FIG. 3 depicts a partial perspective view of a radiator with fins coatedwith a catalyst layer in accordance with an implementation. A radiator300 (which may be the same as radiator the 206 described with respect toFIG. 3B) may include spaced apart tubes 302 for the flow of a firstfluid. The tubes are arranged horizontally through the radiator 300, anda series of corrugated plates 304 are inserted therebetween defining apathway 306 for the flow of a second fluid transverse to the flow of thefirst fluid. The first fluid, such as antifreeze, is supplied from asource to the tubes 302 through an inlet 308. The antifreeze enters theradiator 300 at a relatively low temperature through the inlet 308,eventually leaves the radiator through an outlet 310, and may berecirculated. The second fluid may be ambient air that passes throughthe pathway 306 and exchanges heat with the first fluid passing throughthe tubes 302. The corrugated plates 304 may be coated with base metalcatalyst layers (e.g., the catalyst layer 102 described with respect toFIG. 1) in order to convert or remove pollutants, such as ozone andvolatile organic compounds, from the ambient air. In certainimplementations, the radiator is provided with projections 312 (e.g.,fins), which may be non-heat exchange surfaces directed along theair-flow path. In some implementations, one or more of the projections312 are coated with a catalyst layer as disclosed herein (e.g. byspraying), such as a base metal catalyst. In certain implementations,the projections 312 are omitted.

FIG. 4 depicts a cross sectional view of a catalyst device 400 thatincludes a catalyst layer 402 deposited on a solid substrate 406 inaccordance with an implementation. The catalyst device 400 is formed bycoating a catalyst layer 402 onto the substrate 406, which may includean intervening adhesive layer 404 that adheres the catalyst layer 402 tothe substrate 409. The catalyst layer 402 may be porous and may have ahigh surface area surface 408 that contacts an airstream. The highsurface area surface 408 facilitates turbulent airstream in the vicinityof the catalyst layer 402 such to increase the amount of exposure ofpollutants within the airstream to the catalyst layer 402. The catalystlayer 402 and the adhesive layer 404 are not shown to scale. Amicrograph of a catalyst device formed in accordance with theimplementations described herein is shown in FIG. 5.

In certain implementations, the catalyst layer 402 is a base metalcatalyst. The base metal catalyst is prepared, for example, in the formof a slurry having target amounts of metal salts (e.g., acetate,nitrate, carbonate, sulfate based salts, or potassium permanganate)mixed with a support material (e.g., ceria, lanthana, silica, alumina,or combinations thereof). After addition of one or more binders, theslurry may then be coated onto a substrate (e.g., the substrate 406) andcalcined to produce the catalyst layer.

In some implementations, there may be an overlayer on the catalystcoating or an underlayer between the substrate and the catalyst layer402. The underlayer or overlayer may be a protective coat, an adhesionlayer (e.g., the adhesion layer 404), or an additional catalyst layer.The adhesion layer 404, for example, may be a latex material or anacrylic material. In certain implementations, the catalyst layer 402 isadhered directly to the substrate 406 without the use of the adhesionlayer 404. The protective coat may contain a protective substance whichis stable at elevated temperatures (e.g., up to 120° C.) and may beresistant to chemicals, salts, dirt and other contaminants that mayadversely affect the catalyst composition. The protective material mayinclude, for example, a plastic or polymeric material such aspolyethylene, polypropylene, polytetrafluoroethylene, styrene acrylic,or a combination thereof.

In certain implementations, the catalyst layer 402 is a physical mixtureof metal oxide catalysts particles and high surface area supportparticles such that separate domains of metal oxide and support canfunction independently as catalyst and aging protection, respectively.

In certain implementations, the catalyst layer 402 is an alloy of metaloxide catalysts and high surface area support such that the function ofeach material is inseparable from the other.

In certain implementations, the catalyst layer 402 is a high surfacearea support particle which is in surface contact either within the porestructure and/or externally with small (<100 nm) domains of metal oxidecatalysts such that separate domains of metal oxide can functionindependently as catalyst and are provided protection from agingmechanisms within the support material.

In certain implementations, the catalyst layer 402 is a high surfacearea support particle which is externally coated with a porous shellstructure of metal oxide catalyst material such that the metal oxidecatalyst function is external to the support providing a high surfacearea interior to the composite particle.

In certain implementations, the catalyst layer 402 is a high surfacearea support which is encompassing a metal oxide particle in a coatinglayer such that the metal oxide catalyst is entirely surrounded by aprotective high surface area support material.

In certain implementations, the catalyst layer 402 has a relatively highthermal conductivity while maintaining pollutant destruction efficiency.In certain implementations of the disclosure, high thermal conductivitymaterials (e.g., in the form of particles) may be blended into thecoating to provide or enhance the thermal conductivity property of thecoating without significantly impacting on diffusion through thecoating. Non-limiting examples of such materials include metals such asaluminum, graphite, silicon carbide and sapphire. The material can be inthe form of particles (e.g., flakes). The particle size may be anysuitable size. In one implementation, the particles are on the order ofthe size of the catalyst and/or no more than the desired thickness ofthe coating. For example, the particles may have a mean size from about1 micrometer to about 30 micrometers, or from about 1 micrometer toabout 10 micrometers. The materials (e.g., particles) may be includingin the coating in an amount of from about 1% to about 50% by mass of thetotal coating.

In some implementations, one or more binders may be added to a catalystslurry to enhance washcoat adhesion. In some implementations, twodifferent binders were added to the catalyst slurry, which yieldedimproved performance (in terms of weight loss) over the same quantity ofthe individual binders by themselves. An example catalysis compositionincluded a first styrene acrylic binder (“Binder 1”) and a secondstyrene acrylic binder (“Binder 2”) mixed as shown in Table 1. Binder 1was a styrene acrylic binder (Joncryl® 1530) having a glass transitiontemperature of 12° C. Binder 2 was a styrene acrylic binder (Joncryl®1980) having a glass transition temperature of 78° C. Ultrasonicwashcoat adhesion weight loss testing was performed in accordance withExample 15 discussed below. In some implementations, other types ofbinders may be used.

TABLE 1 Binder Ratios (mass %) and Associated Washcoat Adhesion WeightLoss After Coating Binder Composition Average Loss, % Binder 1 @ 12%2.50 Binder 2 @ 12% 1.70 Binder 1 @ 6% + Binder 2 @ 6% 1.10

In certain implementations of the present disclosure, a catalysiscomposition includes a metal catalyst and support material impregnatedwith the metal catalyst. The catalysis composition further includes afirst binder and a second binder such that a washcoat weight loss of thecatalysis composition after coating onto a substrate is less than about1.6%. In some implementations, the washcoat weight loss of the catalysiscomposition after coating onto the substrate is less than about 1.3%. Insome implementations, the washcoat weight loss of the catalysiscomposition after coating onto the substrate is less than about 1.15%.In one implementation, measuring the washcoat weight loss of thecatalyst layer includes using an ultrasonic adhesion test.

In one implementation, a mass ratio of the first binder to the secondbinder ranges from about 0.75 to about 1.25. In one implementation, atleast one of the first binder or second binder is a styrene acrylicbinder.

In one implementation, the first binder has a first glass transitiontemperature ranging from about 5° C. to about 20° C., and the secondbinder has a second glass transition temperature that is greater thanthe first glass transition temperature. In one implementation, the firstbinder has a first glass transition temperature ranging from about 8° C.to about 15° C., and the second binder has a second glass transitiontemperature that is greater than the first glass transition temperature.

In one implementation, the first binder has a first glass transitiontemperature ranging from about 70° C. to about 90° C., and wherein thesecond binder has a second glass transition temperature that is lessthan the first glass transition temperature. In one implementation, thefirst binder has a first glass transition temperature ranging from about75° C. to about 85° C., and wherein the second binder has a second glasstransition temperature that is less than the first glass transitiontemperature.

In one implementation, the first binder has a first glass transitiontemperature ranging from about 5° C. to about 20° C., and the secondbinder has a second glass transition temperature ranging from about 70°C. to about 90° C. In one implementation, the first binder has a firstglass transition temperature ranging from about 8° C. to about 15° C.,and the second binder has a second glass transition temperature rangingfrom about 75° C. to about 85° C.

In one implementation, a first mass percent of the first binder withinthe catalysis composition is between about 4% and about 8%, and a secondmass percent of the second binder within the catalysis composition isbetween about 4% and about 8%.

The following examples are set forth to assist in understanding theinvention and should not, of course, be construed as specificallylimiting the invention described and claimed herein. Such variations ofthe invention, including the substitution of all equivalents now knownor later developed, which would be within the purview of those skilledin the art, and changes in formulation or minor changes in experimentaldesign, are to be considered to fall within the scope of the inventionincorporated herein.

ILLUSTRATIVE EXAMPLES Example 1

A manganese nitrate solution (50% w/w solution) was diluted to a volumematching the incipient wetness point of a high surface area gammaalumina support material (2.0 mL/g), referred to hereinafter as“Support(1)”, and to a concentration matching the total desiredmanganese (Mn) content of the final solid (5.0 g of Mn). Support(1) is agamma alumina and silica (19:1) support, and, as measured, has a BETsurface area of 230 m²/g, a pore volume of 1.2 mL/g, and average poreradius of 7.5 nanometers. The diluted Mn nitrate solution was slowly andcompletely added to the dry Support(1) solid (92.1 g) under mixing untilreaching the incipient wetness point, forming Mn impregnated wetalumina. The Mn impregnated wet alumina was dried at 90° C. for 2 hours,and then calcined at 550° C. in a box furnace for one hour.

Example 2

A manganese nitrate solution (50% w/w solution) was diluted to a volumematching the incipient wetness point of Support(1) (2.0 mL/g), and to aconcentration matching the total desired Mn content of the final solid(15.0 g of Mn). The diluted Mn nitrate solution was slowly andcompletely added to the dry Support(1) solid (76.3 g) under mixing untilreaching the incipient wetness point, forming Mn impregnated wetalumina. The Mn impregnated wet alumina was then dried at 90° C. for 2hours and then calcined at 550° C. in a box furnace for one hour.

Example 3

A manganese acetate solution (30% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100 mL of deionized water. The Mnacetate solution was diluted to a volume matching the incipient wetnesspoint of Support(1) (2.0 mL/g), and to a concentration matching thetotal desired Mn content of the final solid (5.0 g of Mn). The dilutedMn acetate solution was slowly and completely added to dry Support(1)solid (92.1 g) under mixing until reaching the incipient wetness point,forming Mn impregnated wet alumina. The Mn impregnated wet alumina wasthen dried at 90° C. for 2 hours and then calcined at 550° C. in a boxfurnace for one hour.

Example 4

A manganese acetate solution (30% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100 mL of deionized water. The Mnacetate solution was diluted to a volume matching the incipient wetnesspoint of Support(1) (2.0 mL/g), and to a concentration matching thetotal desired Mn content of the final solid (15.0 g of Mn). The dilutedMn acetate solution was slowly and completely added to the drySupport(1) solid (76.3 g) under mixing until reaching the incipientwetness point, forming Mn impregnated wet alumina. The Mn impregnatedwet alumina was then dried at 90° C. for 2 hours and then calcined at550° C. in a box furnace for one hour.

Example 5

A manganese acetate solution (30% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100 mL of deionized water. Themanganese acetate solution was diluted into two separate solutions, eachto volumes matching the incipient wetness point of a gamma aluminasupport material (1.1 mL/g), hereinafter referred to as “Support(2)”,and to a concentration matching half the total desired Mn content of thefinal solid (14.0 g of Mn). Support(2) is a high surface area gammaalumina and silica (19:1) support with a measured BET surface area of320 m²/g and a Barrett-Joyner-Halenda (BJH) pore volume of 0.8 mL/g. Thediluted Mn acetate solution was slowly and completely added to the drySupport(2) solid (76.3 g) under mixing until reaching the incipientwetness point, forming Mn impregnated wet alumina. The Mn impregnatedwet alumina was then dried at 90° C. for 2 hours, and then theimpregnation procedure was repeated with the second Mn acetate solutionin the same manner. The final wet alumina was then dried at 90° C. for 2hours and then calcined at 550° C. in a box furnace for one hour.

Example 6

A solution containing manganese (30% w/w solution) and potassium (15%w/w solution) was prepared by dissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100mL of deionized water and K(C₂H₃O₂) (18 g) in 100 mL of deionized water.The manganese and potassium solution was diluted to a volume matchingthe incipient wetness point of Support(1) (2.0 mL/g) and to aconcentration matching the total desired Mn content of the final solid(15.0 g of Mn). The diluted Mn and K acetate solution was slowly andcompletely added to the dry Support(1) solid (76.3 g) under mixing untilreaching the incipient wetness point, forming Mn/K impregnated wetalumina. The Mn/K impregnated wet alumina was then dried at 90° C. for 2hours and then calcined at 550° C. in a box furnace for one hour.

Example 7

A cobalt (Co) nitrate solution (20% w/w solution) was prepared bydissolving Co(NO₃)₂.6H₂O (60 g) in 100 mL of deionized water. The cobaltnitrate solution was diluted to a volume matching the incipient wetnesspoint of Support(1) (2.0 mL/g) and to a concentration matching the totaldesired Co content of the final solid (5.0 g of Co). The diluted Conitrate solution was slowly and completely added to the dry Support(1)solid (93.2 g) under mixing until reaching the incipient wetness point,forming Co impregnated wet alumina. The Co impregnated wet alumina wasthen dried at 90° C. for 2 hours and then calcined at 550° C. in a boxfurnace for one hour.

Example 8

A manganese acetate solution (30% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100 mL of deionized water. Themanganese acetate solution was diluted to volume matching the incipientwetness point of a gamma alumina support material (1.4 mL/g),hereinafter referred to as “Support(3)”, and to concentration matchingthe total desired Mn content of the final solid (5.0 g of Mn).Support(3) is a high surface area gamma alumina and silica (19:1)support with measured BET surface area of 180 m²/g and a BJH pore volumeof 0.85 mL/g. The diluted Mn acetate solution was slowly and completelyadded to the dry Support(3) solid (92.1 g) under mixing until reachingthe incipient wetness point, forming Mn impregnated wet alumina. The Mnimpregnated wet alumina was then dried at 90° C. for 2 hours and thencalcined at 550° C. in a box furnace for one hour.

Example 9

A manganese acetate solution (30% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100 mL of deionized water. Themanganese acetate solution was diluted to a volume matching theincipient wetness point of a silica support material (2.76 mL/g),hereinafter referred to as “Support(4)”, and to a concentration matchingthe total desired Mn content of the final solid (5.0 g of Mn).Support(4) is a high surface area silica support as measured has a BETsurface area of 200 m²/g. The diluted Mn acetate solution was slowly andcompletely added to the dry Support(4) solid (92.1 g) under mixing untilreaching the incipient wetness point, forming Mn impregnated wet silica.The Mn impregnated wet silica was then dried at 90° C. for 2 hours andthen calcined at 550° C. in a box furnace for one hour.

Example 10

A manganese acetate solution (30% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (60 g) in 100 mL of deionized water. Themanganese acetate solution was diluted to a volume matching theincipient wetness point of Support(1) (2.0 mL/g) and to a concentrationmatching the total desired Mn content of the final solid (15.0 g of Mn).The diluted Mn acetate solution was slowly and completely added to thedry Support(1) solid (76.3 g) under mixing until reaching the incipientwetness point, forming Mn impregnated wet alumina. The Mn impregnatedwet alumina was then fed directly into a flash calcination reaching 550°C. in under 1 minute.

Example 11

A manganese nitrate solution (50% w/w solution) was diluted to a volumematching the incipient wetness point of Support(1) (2.0 mL/g) and to aconcentration matching the total desired Mn content of the final solid(15.0 g of Mn). The diluted Mn nitrate solution was slowly andcompletely added to the dry Support(1) solid (76.3 g) under mixing untilreaching the incipient wetness point, forming Mn impregnated wetalumina. The Mn impregnated wet alumina was then fed directly into aflash calcination reaching 550° C. in under 1 minute.

Example 12

A manganese acetate solution (15% w/w solution) was prepared bydissolving Mn(C₂H₃O₂)₂.4H₂O (67 g) in 225 mL of deionized water. The Mnacetate solution was mixed with Support(1) (76.3 g) to form a slurrywith a concentration of Mn matching the total desired Mn content of thefinal solid (15.0 g of Mn). The diluted Mn acetate and Support(1) slurrywas dried at 90° C. and then calcined at 550° C. in a box furnace forone hour.

Example 13

A catalyst was prepared using bulk manganese oxide powder with highsurface area with a BET surface area of 240 m²/g and a BJH pore volumeof 0.39 mL/g. This Mn oxide catalyst is of a cryptomelane type structureas described in U.S. Pat. No. 6,517,899.

Example 14 Catalyst Slurry Composition

Catalysts prepared according to Examples 3, 4, and 10-13 were used toprepare water based slurries for coating of substrates. Dry catalystsolids were mixed with polyacid dispersant (Rhodoline® 226/35 at 5% drysolids based on catalyst) and water (total solids about 30%) in a ballmill apparatus. The slurry was ball milled to a particle size of 50%<5micrometers. The ball milled material was then blended with a styreneacrylic binder in a water based slurry (at 10% dry solids based oncatalyst) to form a slurry with minimal adhesion properties for coatingof substrates. Additional slurry components (such as xanthum gum andother surfactants) at levels <1% dry solids including binders,dispersants, and suspension aids were selected from those included inU.S. Pat. No. 6,517,899, which is hereby incorporated by referenceherein in its entirety. The compositions were coated onto radiatorsegments of an aluminum Mitsubishi Radiator (Denso Part # AA422133-0501)using a hand dip procedure. Radiator segments (about 0.5 in² frontalsurface area) were dipped in catalyst slurries, and the excess was blownout with an air gun and dried at 90° C. with target dry gain loadings of0.40 g/in³.

Example 15 Ultrasonic Adhesion Testing Method

Catalyst compositions prepared according to example 14 were tested foradhesion according to an ultrasonic procedure method. Coated radiatorsegments were immersed in deionized water and exposed to ultrasonicwaves at 25 kHz and 500 Watts for 5 minutes. The segments were thendried at 90° C., and the weight difference before and after ultrasonictreatment was measured determining the total loss of coated materialrelative to the initial weight of the coated segment using a triplicatesample set.

Example 16 Catalyst Powder Ozone Conversion Testing Method

A powder testing method in which the catalyst materials preparedaccording to examples 1-13 were exposed to an airstream containing agiven concentration of ozone (about 0.6 ppm to about 0.9 ppm). A sampleof 20 mg of catalyst material was pelletized and sieved between 250micrometer and 425 micrometer particles, and then mixed with an inertmaterial to a volume of about 0.33 mL. Ozone concentration levels in theairstream, flowed at a space velocity of about 1,500,000 hr⁻¹ and atemperature of 35° C., were measured before and after the exposure tothe catalyst powder. As used herein, “space velocity” refers to avolumetric ratio of an airstream flow to volume of a catalyst-coatedsubstrate.

Example 17 Catalyst Powder Ozone Conversion Testing Results

Results shown in Table 2 below indicate that Example 4 has the highestactivity according to the powder testing method of Example 16. Incomparing Examples 2 and 4, as well as Examples 1 and 3, resultsindicate the Mn acetate solution used for Mn impregnation producescatalysts more active for ozone conversion than those prepared using Mnnitrate solutions. In addition, it was demonstrated that higher levelsof Mn on the catalyst support produce catalysts that are more active forozone conversion.

TABLE 2 Ozone Conversion Sample Ozone Conversion, % Example 1 19.1Example 2 28.8 Example 3 30.9 Example 4 35.9

Example 18 Radiator Ozone Conversion Testing Method

Catalyst slurry compositions were prepared according to example 14 forcatalysts 3, 4, and 10-13 and tested with an airstream containing agiven concentration of ozone (about 0.1 ppm to about 1.2 ppm) passedthrough the coated radiator segments at face velocities typical ofdriving speeds (ranging from about 15 mph to about 30 mph). Ozoneconcentration levels in the airstream were measured before and after thecoated radiator segment. The air temperature was maintained at about 75°C. with humidity dewpoint levels at both −15° C. and +15° C.

Example 19 Accelerated Aging (150 k) Method

In referring to the term “deactivation factor, as it applies toautomobile radiator coatings, the “aged % conversion” is defined (incertain implementations) as the percent conversion after the exposure tothe equivalent of 150,000 miles of driving time. In order to rapidlysimulate the effects of 150,000 miles of driving exposure, anaccelerated aging test for catalyst coatings is employed. The coatedradiator segment is inserted into an enclosed system with a controlledairstream that contains a high concentration of aerosol particles thatis flowed over the radiator over a shortened period of time. Initially,of two radiators coated using identical methods, such as modifiedprocedures as described in U.S. Pat. No. 6,517,899 and U.S. Pat. No.6,555,079 (both of which hereby incorporated by reference herein intheir entireties), one coated radiator was exposed to 150,000 miles ofon road aging and the other exposed to the accelerated aging test. As anexample, a Ford Taurus radiator with a 1″ depth and 49 cells per squareinch (cpsi) was exposed to the accelerated aging test and exhibited adeactivation factor 0.49. This accelerated aging test provides the aged% conversion value necessary for calculating the deactivation factorsillustrated in FIGS. 6A and 6B. FIG. 6A corresponds to aging testresults for a 16 mm depth radiator with 63 cpsi. FIG. 6B corresponds toaging test results for a 26 mm depth radiator with 49 cpsi. In bothtests, Example 4 had the best performance after aging.

Example 20 Morphological Analysis

Various physical properties of manganese-based catalysis compositionswere measured, including manganese content, surface area, pore volume,average pore radius, manganese structure, and manganese dispersion. Someof these properties are summarized for various example compositions inTable 3 below. Overall manganese content was determined by measuringx-ray fluorescence (XRF). In some implementations, a catalysiscomposition included a manganese content (mass %) ranging from about 14%to about 16%. In some implementations, the manganese content ranges fromabout 12% to about 18%. In some implementations, the manganese contentranges from about 5% to about 30%. In some implementations, themanganese content ranges from about 10% to about 25%.

TABLE 3 Catalyst Morphological Properties Mn Surface Pore Avg. PoreContent Area volume Radius Mn (XRF), (BET), (BJH), (BJH), SamplePrecursor % m²/g mL/g nm Example 4 Acetate 14.78 193.8 0.90 7.65 Example10 Nitrate 14.26 222.7 0.73 5.26 Example 11 Acetate 12.82 219.4 0.775.59 Example 12 Acetate 14.68 188.1 0.86 6.98

X-ray photoelectron spectroscopy (XPS) was used to measure the surfaceMn content of various catalysis compositions. XPS provides a measure ofthe Mn dispersion by comparing a mass of Mn detectable near the surfaceof the catalysis composition (e.g., within about 10 nanometers of thesurface) versus the overall mass of Mn contained in the bulk (referredto herein as a “dispersion ratio”). Catalysis compositions, as preparedin accordance with the implementations described herein, may havedispersion ratios of at least about 13%. In some implementations, thedispersion ratio is at least about 15%. In some implementations, thedispersion ratio is at least about 30%. In some implementations, thedispersion ratio is at least about 50%.

XPS measurements were conducted using a K-Alpha™⁺ x-ray photoelectronspectrometer system (Thermo Scientific) with an aluminium K-α X-raysource. Powder samples were loaded onto carbon tape and outgassed for 2hours prior to analysis. After an initial survey scan of the samplesurface from 0-1350 eV, targeted high resolution scans of identifiedelements were conducted using a constant pass energy of 40.0 eV. Thebinding energies were referenced to the adventitious C1s peak, 284.8 eV.Shirley background and mixed Gaussian-Lorentzian line shapes were usedto fit the resulting XPS spectra. Relative atomic percentages were thendetermined using the fitted peak data and sensitivity factors of eachelement (provided by Avantage software).

The pore structure of the supported catalyst, including both the porevolume and pore width, as well as surface area of the catalysiscompositions were measured using a Micrometrics® TriStar 3000 Seriesinstrument. Samples were prepared using an initial degassing cycle underN₂ with a 2 hour ramp rate up to 300° C. and a 4 hour soak time at 300°C. For surface area values, a 5 point BET measurement was used withpartial pressures of 0.08, 0.11, 0.14, 0.17, and 0.20. Cumulative porevolume and average pore radius measurements were obtained from a BJHmultipoint N₂ desorption/adsorption isotherm analysis using only poreswith radii between 1.0 and 30.0 nm.

Using x-ray diffraction (XRD), the resulting spectra showedcharacteristic peaks of small manganese oxide crystallites. FIG. 7Ashows a control spectrum corresponding to Support(1). FIGS. 7B and 7Care spectra corresponding to Examples 3 and 4, respectively, with peaksrepresentative of Support(1) being present in each. As shown in FIG. 7B,peaks 702, 704, 706 are representative of pyrolusite (MnO₂)crystallites, while peaks 712, 714, 716 are representative of bixbyite(Mn₂O₃) crystallites. As shown in FIG. 7C, peaks 752, 754, 756 arerepresentative of hausmannite (Mn₃O₄) crystallites. XRD measurementswere obtained from powder samples using a PANalytical X'Pert Pro MPDdiffraction system collecting data in Bragg-Brentano geometry, usingCu_(Kα) radiation in the analysis with generator settings of 45 kV and40 mA. Data was collected from 10° to 90° 2θ using a step size of 0.026°2θ and a count time of 600 s per step. Jade Plus 9 analytical XRDsoftware was used for phase identification.

The manganese oxide structure of certain catalysis compositions wasmeasured by XRD. Some catalysis compositions had crystallites that werenearly undetectable by XRD. In some implementations, the catalysiscomposition performance (e.g., in terms of ozone conversion) appeared tobe greater for catalysis compositions with smaller crystallite sizes(e.g., less than 10 nm). Without being bound by theory, it is believedthat larger crystallite domains correspond to poorly dispersed magnesiumoxide. In some implementations, manganese oxide crystallites includedone or more of hausmannite (Mn₃O₄), manganosite (MnO), bixbyite (Mn₂O₃),or pyrolusite (MnO₂).

An estimate of crystallite size can be computed based on the Scherrerequation:

${\tau = \frac{K\; \lambda}{\beta \; \cos \; \theta}},$

where:τ is the average size of the crystalline domains;K is a dimensionless shape factor, with a value close to unity(typically assumed to be 0.9);λ is the x-ray wavelength;β is the line broadening at half the maximum intensity (FWHM), aftersubtracting the instrumental line broadening, in radians; andθ is the Bragg angle.

The FWHM of the characteristic peaks in the 2θ range of 30° to 50° wasused in the Scherrer equation to estimate crystallite size, as shown inTable 4. In some implementations, the average crystallite size was lessthan 30 nm, less than 20 nm, or less than 10 nm.

TABLE 4 Crystallite Sizes as Measured by XRD Mn₂O₃ Crystallite MnO₂Crystallite Mn₃O₄ Crystallite Sample Size (nm) Size (nm) Size (nm)Example 3 26.4 8.6 — Example 4 — — 9.4

Additional Implementations

FIG. 8 is a flow diagram illustrating a method 800 for producing acatalyst device in accordance with an implementation. At block 802, aslurry is provided. The slurry includes a metal catalyst and a supportmaterial impregnated with the metal catalyst. In one implementation, theslurry contains additional metal oxide catalysts, or one or moremetal-based catalysts in lieu of a metal oxide catalyst. The slurry maybe prepared in accordance with any of the implementations describedherein. In one implementation, the metal oxide catalyst is at leastpartially derived from a manganese acetate precursor.

In one implementation, the metal oxide catalyst is impregnated in thesupport material in an amount of about 1 atom to about 1.5 atoms persurface hydroxyl group of the support material. In one implementation,the metal oxide catalyst includes a base metal oxide selected from agroup consisting of iron, copper, chromium, zinc, manganese, cobalt,nickel, compounds containing the same, and combinations thereof. In oneimplementation, the support material is selected from a group consistingof ceria, lanthana, alumina, titania, silica, zirconia, carbons, metalorganic framework, clay, zeolites, and combinations thereof.

In one implementation, the metal oxide catalyst is impregnated in thesupport material such that at least about 15% of a total number of atomsin the metal oxide catalyst are detectable by surface XPS. In oneimplementation, the catalyst is impregnated in the support material suchthat at least about 30% of the total number of atoms in the metal oxidecatalyst are detectable by surface XPS. In one implementation, the metaloxide catalyst is impregnated in the support material such that at leastabout 50% of the total number of atoms in the metal oxide catalyst aredetectable by surface XPS. In one implementation, all atoms detectableby surface XPS are within about 10 nanometers from a surface of thecatalysis composition at which the surface XPS is performed.

In one implementation, a cumulative pore volume of the catalysiscomposition is at least about 0.60 mL/g. In one implementation, thecumulative pore volume of the catalysis composition is at least about0.70 mL/g. In one implementation, the cumulative pore volume of thecatalysis composition is at least about 0.80 mL/g. In oneimplementation, the cumulative pore volume of the catalysis compositionis at least about 0.85 mL/g. In one implementation, an average poreradius of the catalysis composition ranges from about 6 nanometers toabout 15 nanometers. In one implementation, the average pore radius ofthe catalysis composition ranges from about 6 nanometers to about 10nanometers. In one implementation, the average pore radius of thecatalysis composition ranges from about 6 nanometers to about 8nanometers. In one implementation, an average pore volume of the metalcatalyst is greater than 0.70 mL/g.

In one implementation, the metal oxide catalyst includes manganese oxidecrystallites. In one implementation, the metal oxide catalyst includesat least one of Mn₃O₄ crystallites or MnO crystallites. In oneimplementation, an x-ray diffraction spectrum of the catalysiscomposition includes at least one characteristic peak including at leastone of a manganosite peak, pyrolusite peak, a bixbyite peak, or ahausmannite peak. In one implementation, the at least one characteristicpeak includes a pyrolusite peak and a bixbyite peak. In oneimplementation, the at least one characteristic peak includes apyrolusite peak and a hausmannite peak. In one implementation, the atleast one characteristic peak includes a bixbyite peak and a hausmannitepeak. In one implementation, the at least one characteristic peakincludes a bixbyite peak, a pyrolusite peak, and a hausmannite peak. Inone implementation, the characteristic peaks correspond to crystallitedomains having average diameters of less than about 20 nanometers (e.g.,as determined using the Scherrer equation).

In one implementation, the catalysis composition, when coated onto asubstrate and contacted with an airstream having an initial ozoneconcentration, is adapted to convert ozone within the airstream suchthat a final ozone concentration of the airstream is reduced by greaterthan 30% of the initial ozone concentration after the catalysiscomposition is contacted with the airstream. In some implementations,the final ozone concentration of the airstream is reduced by greaterthan 40% of the initial ozone concentration. In some implementations,the final ozone concentration of the airstream is reduced by greaterthan 50% of the initial ozone concentration. In some implementations,the final ozone concentration of the airstream is reduced by greaterthan 60% of the initial ozone concentration. In some implementations,the final ozone concentration of the airstream is reduced by greaterthan 70% of the initial ozone concentration. In some implementations,final ozone concentration of the airstream is reduced by greater than80% of the initial ozone concentration. In some implementations, thefinal ozone concentration of the airstream is reduced by greater than90% of the initial ozone concentration. In one implementation, theinitial ozone concentration ranges from about 0.1 ppm to about 1.2 ppm.In one implementation, the initial ozone concentration ranges from about0.1 ppm to about 0.9 ppm. In one implementation, the initial ozoneconcentration ranges from about 0.6 ppm to about 0.9 ppm. In oneimplementation, a space velocity of the airstream ranges from about200,000 hr⁻¹ to about 800,000 hr⁻¹. In one implementation, a temperatureof the airstream is maintained within a range of about 70° C. to about80° C.

In one implementation, a surface area of the catalysis composition is atleast about 50 m²/g. In one implementation, the surface area is at leastabout 100 m²/g. In one implementation, the surface area is at leastabout 160 m²/g. In one implementation, the surface area ranges fromabout 50 m²/g to about 5000 m²/g. In one implementation, the surfacearea ranges from about 100 m²/g to about 300 m²/g. In oneimplementation, the surface area ranges from about 100 m²/g to about 200m²/g.

At block 804, the slurry is coated onto a substrate. In oneimplementation, the substrate is an automobile component selected from agroup consisting of vehicle paint, a wheel well, a bumper, an airconditioning component, a grille, a fan, a fan blade, a shroud, ashutter, a turbo intercooler, a gear box cooler, a front end component,a radiator, and a hood liner. In one implementation, the catalysiscomposition, when coated onto the substrate, has a deactivation factorof at least 0.5. In one implementation, coating the slurry onto thesubstrate includes dipping the substrate into the slurry.

At block 806, the slurry is dried to produce a catalyst layer. In oneimplementation, coating the slurry onto the substrate includes dryingthe slurry at a temperature ranging from about 80° C. to about 120° C.to produce the catalyst layer. In one implementation, a washcoatadhesion weight loss of the substrate is measured using an ultrasonicadhesion test.

At block 808, the catalyst layer is contacted with an airstream. In oneimplementation, the contacting of the catalyst layer with the airstreamis performed by operating the automobile. In one implementation, thecontacting of the catalyst layer with the airstream is performed using atesting apparatus.

For simplicity of explanation, the embodiments of the methods of thisdisclosure are depicted and described as a series of acts. However, actsin accordance with this disclosure can occur in various orders and/orconcurrently, and with other acts not presented and described herein.Furthermore, not all illustrated acts may be required to implement themethods in accordance with the disclosed subject matter. In addition,those skilled in the art will understand and appreciate that the methodscould alternatively be represented as a series of interrelated statesvia a state diagram or events.

In the foregoing description, numerous specific details are set forth,such as specific materials, dimensions, processes parameters, etc., toprovide a thorough understanding of the present invention. Theparticular features, structures, materials, or characteristics may becombined in any suitable manner in one or more embodiments. The words“example” or “exemplary” are used herein to mean serving as an example,instance, or illustration. Any aspect or design described herein as“example” or “exemplary” is not necessarily to be construed as preferredor advantageous over other aspects or designs. Rather, use of the words“example” or “exemplary” is intended to present concepts in a concretefashion. As used in this application, the term “or” is intended to meanan inclusive “or” rather than an exclusive “or”. That is, unlessspecified otherwise, or clear from context, “X includes A or B” isintended to mean any of the natural inclusive permutations. That is, ifX includes A; X includes B; or X includes both A and B, then “X includesA or B” is satisfied under any of the foregoing instances. In addition,the articles “a” and “an” as used in this application and the appendedclaims should generally be construed to mean “one or more” unlessspecified otherwise or clear from context to be directed to a singularform. Reference throughout this specification to “an implementation”,“certain implementations”, or “one implementation” means that aparticular feature, structure, or characteristic described in connectionwith the implementation is included in at least one implementation.Thus, the appearances of the phrase “an implementation”, “certainimplementations”, or “one implementation” in various places throughoutthis specification are not necessarily all referring to the sameimplementation.

The term “about”, when referring to a physical quantity, is to beunderstood to include measurement errors within, and inclusive of 2%.For example, “about 100° C.” should be understood to mean “100±1° C.”

The present invention has been described with reference to specificexemplary embodiments thereof. The specification and drawings are,accordingly, to be regarded in an illustrative rather than a restrictivesense. Various modifications of the invention in addition to those shownand described herein will become apparent to those skilled in the artand are intended to fall within the scope of the appended claims.

What is claimed is:
 1. A catalysis composition comprising: a metal oxidecatalyst comprising manganese oxide, wherein an x-ray diffractionspectrum of the catalysis composition comprises at least onecharacteristic peak comprising at least one of a manganosite peak,pyrolusite peak, a bixbyite peak, or a hausmannite peak; and a supportmaterial impregnated with the metal oxide catalyst.
 2. The catalysiscomposition of claim 1, wherein the metal oxide catalyst is impregnatedin the support material in an amount ranging from about 5% to about 30%by mass, about 10% to about 25% by mass, or about 12% to about 18% bymass.
 3. The catalysis composition of claim 1, wherein the at least onecharacteristic peak of the x-ray diffraction spectrum corresponds tocrystallite domains having average diameters of less than about 20nanometers.
 4. The catalysis composition of claim 1, wherein the atleast one characteristic peak comprises a pyrolusite peak and a bixbyitepeak.
 5. The catalysis composition of claim 1, wherein the at least onecharacteristic peak comprises a pyrolusite peak and a hausmannite peak.6. The catalysis composition of claim 1, wherein the at least onecharacteristic peak comprises a bixbyite peak and a hausmannite peak. 7.The catalysis composition of claim 1, wherein the at least onecharacteristic peak comprises a bixbyite peak, a pyrolusite peak, and ahausmannite peak.
 8. The catalysis composition of claim 1, wherein themetal oxide catalyst is impregnated in the support material such that atleast about 15% of a total number of metal atoms in the metal oxidecatalyst are detectable by surface x-ray photoelectron spectroscopy(XPS).
 9. The catalysis composition of claim 1, wherein the metal oxidecatalyst was at least partially derived from a manganese acetateprecursor.
 10. The catalysis composition of claim 1, wherein the supportmaterial is selected from a group consisting of ceria, lanthana,alumina, titania, silica, zirconia, carbons, metal organic framework,clay, zeolites, and combinations thereof.
 11. The catalysis compositionof claim 1, wherein a surface area of the catalysis composition is atleast about 160 m²/g.
 12. The catalysis composition of claim 1, whereina cumulative pore volume of the catalysis composition is greater than0.70 mL/g.
 13. The catalysis composition of claim 1, wherein acumulative pore volume of the catalysis composition is greater than 0.80mL/g.
 14. The catalysis composition of claim 1, wherein an average poreradius of the catalysis composition ranges from about 6 nanometers toabout 15 nanometers.
 15. The catalysis composition of claim 1, whereinthe catalysis composition, when coated onto a substrate and contactedwith an airstream having an initial ozone concentration, is adapted toconvert ozone within the airstream such that a final ozone concentrationof the airstream is reduced by greater than 30% of the initial ozoneconcentration after the catalysis composition is contacted with theairstream.
 16. The catalysis composition of claim 1, wherein catalysiscomposition is coated onto an automobile component selected from a groupconsisting of vehicle paint, a wheel well, a bumper, an air conditioningcomponent, a grille, a fan, a fan blade, a shroud, a shutter, a turbointercooler, a gear box cooler, a battery cooler, a front end component,a radiator, and a hood liner.
 17. The catalysis composition of claim 1,further comprising: a first binder; and a second binder.
 18. Thecatalysis composition of claim 17, wherein the first binder is a styreneacrylic binder having a first glass transition temperature ranging fromabout 5° C. to about 20° C., and wherein the second binder is a styreneacrylic binder having a second glass transition temperature ranging fromabout 70° C. to about 90° C.
 19. The catalysis composition of claim 1,wherein the catalysis composition, when coated onto a substrate, has adeactivation factor of at least about 0.5.
 20. The catalysis compositionof claim 1, wherein the metal oxide catalyst comprises a base metaloxide selected from a group consisting of iron, copper, chromium, zinc,manganese, cobalt, nickel, compounds containing the same, andcombinations thereof.
 21. The catalysis composition of claim 1, whereinthe support material is selected from a group consisting of ceria,lanthana, alumina, titania, silica, zirconia, carbons, metal organicframework, clay, zeolites, and combinations thereof.
 22. A catalysisdevice comprising: an automobile component; and the catalysiscomposition of claim 1, wherein the catalysis composition is coated ontothe automobile component.
 23. A method comprising: providing a slurry ofa catalysis composition, wherein the catalysis composition comprises: ametal oxide catalyst; and a support material impregnated with the metaloxide catalyst, wherein an x-ray diffraction spectrum of the catalysiscomposition comprises at least one characteristic peak comprising atleast one of a manganosite peak, pyrolusite peak, a bixbyite peak, or ahausmannite peak; and coating the slurry onto a substrate to produce acatalyst layer.
 24. The method of claim 23, wherein the at least onecharacteristic peak comprises a pyrolusite peak and a bixbyite peak. 25.The method of claim 23, wherein the at least one characteristic peakcomprises a pyrolusite peak and a hausmannite peak.
 26. The method ofclaim 23, wherein the at least one characteristic peak comprises abixbyite peak and a hausmannite peak.
 27. The method of claim 23,wherein the at least one characteristic peak comprises a bixbyite peak,a pyrolusite peak, and a hausmannite peak.
 28. The method of claim 23,wherein a surface area of the catalysis composition is at least about160 m²/g.
 29. The method of claim 23, wherein coating the slurry ontothe substrate comprises drying the slurry at a temperature ranging fromabout 80° C. to about 120° C. to produce the catalyst layer.
 30. Themethod of claim 23, wherein the substrate is a component of anautomobile, and wherein the component is selected from a groupconsisting of vehicle paint, a wheel well, a bumper, an air conditioningcomponent, a grille, a fan, a fan blade, a shroud, a shutter, a turbointercooler, a gear box cooler, a battery cooler, a front end component,a radiator, and a hood liner.